Semiconductor device formed on (111) surface of a Si crystal and fabrication process thereof

ABSTRACT

A semiconductor device includes a Si crystal having a crystal surface in the vicinity of a (111) surface, and an insulation film formed on said crystal surface, at least a part of said insulation film comprising a Si oxide film containing Kr or a Si nitride film containing Ar or Kr.

CROSS REFERENCE TO RELATED APPLICATIONS

The present invention is based on Japanese patent application 11-376170filed on Nov. 30, 1999, the entire contents thereof being incorporatedherein by reference.

BACKGROUND OF THE INVENTION

The present invention generally relates to semiconductor devices andmore particularly to a semiconductor device formed on a (111) surface ofa Si crystal and fabrication process thereof.

A gate insulation film of a MIS (metal/semiconductor/Si) transistor issubjected to various stringent requirements with regard to electricproperties, including low leakage current, small surface state density,large hotcarrier resistance, and the like. Further, such a gateinsulation film is required to provide high reliability. In order tomeet for these stringent demands, it has been practiced conventionallyto form the gate insulation film by a thermal oxidation of a Sisubstrate surface at a temperature of 800° C. or more.

However, a satisfactory oxide film that satisfies the requirements withregard to interface characteristics of the oxide/Si substrate interface,breakdown characteristics, and leakage current characteristics, isobtained only when the surface of the Si substrate has a (100)orientation as far as thermal oxidation process is used. When a thermaloxidation process is applied to a Si substrate having a surfaceorientation other than the (100) surface for forming a gate oxide film,there arises various problems in the gate oxide film such as increasedsurface state density at the oxide/Si substrate interface as comparedwith case of forming the Si oxide film on the (100)-oriented Sisubstrate. Further, the oxide film thus formed suffers from the problemof poor breakdown voltage characteristics or poor leakage currentcharacteristics.

With regard to mobility, a MIS transistor shows a large mobility whenformed on the (100)-oriented Si substrate. On the other hand, it is notpossible to form a MIS transistor having a large driving power on a Sisubstrate having a different surface orientation.

Meanwhile, there is a need of introducing a metal material into asemiconductor substrate in high-speed semiconductor devices operablewith a clock rate of about 10 GHz, for realizing attenuation-free signaltransmission and cross-talk suppression. However, the use of hightemperature process that requires a temperature of 550° C. or more inthe device fabrication process raises the problem of deterioration ofdevice performance caused by reaction between the metal layer and thesemiconductor layer. Further, the use of high-temperature annealingprocess tends to facilitate diffusion of impurity elements introducedinto the active region of the semiconductor layer, and there arises adifficulty in controlling the impurity distribution profile accurately.Thus, it has been necessary to avoid the use of thermal oxidationprocess conducted at the temperature of 800° C. or more in thefabrication process of highly miniaturized high-speed semiconductordevices.

Meanwhile, it is desirable to form a semiconductor device on a (111)surface of a Si crystal, in which Si atoms are arranged with a largesurface density, in order to improve the driving power of thesemiconductor device. Further, there is a demand of using a very thingate insulation film having a dielectric constant larger than that of aSi oxide film. However, there has been no known process that enablesformation of a high-quality high-dielectric film having a small surfacestate density and excellent electric property on a (111) surface of a Sicrystal at low temperature.

In recent high-density semiconductor integrated circuits, it isgenerally practiced to form a shallow trench isolation (STI) structureon a Si substrate. In a semiconductor integrated circuit having such anSTI structure, there arises a problem in that the thickness of an Sioxide film formed by a thermal oxidation process is tend to be reducedat the corner part of the device isolation groove as compared with theflat surface of the Si substrate. Associated therewith, the quality ofthe Si oxide film is deteriorated in such a corner part. Thus, there hasbeen a reliability problem in the conventional semiconductor integratedcircuit devices that uses an STI structure, such as degradation ofleakage current characteristic or degradation of breakdowncharacteristic, particularly at the corner part of the STI structure. Itis believed that the foregoing problem is caused by the (111) surfacethat appears at such a corner part of the device isolation groove whenthe device isolation groove is formed in an ordinary Si substrate havingthe (100) surface.

In order to avoid the foregoing problem, it has been practicedconventionally to form the STI structure such that the device isolationgroove constituting the STI structure has a sidewall inclined withrespect to the surface of the Si substrate with an angle of about 70degrees or less. In other words, it has been practiced to provide ataper angle to the device isolation groove of the STI structure forminimizing the thinning of the Si oxide film at the corner part of thedevice isolation groove. In spite of such a measure, however, it has notbeen successful to suppress the degree of decrease of the film thicknessbelow about 30%, and thus, the problem of increased leakage current ordegradation of breakdown characteristic of the oxide film in the thinnedpart thereof has not been overcome. Further, the device having such atapered device isolation groove has a drawback of increased width of thedevice isolation groove, and associated problem of reduced effectivearea on which semiconductor devices such as a transistor are formed.Thereby, increase of integration density of the semiconductor integratedcircuit device has been impeded.

A polysilicon film formed on an insulation film shows a tendency thatthe Si crystals therein are oriented generally in the <111> direction.As long as conventional thermal oxidation process is used, it has beendifficult to form a high-quality silicon gate oxide film on such apolysilicon film having the preferred orientation in the <111>direction. Thus, it has been difficult to form a high-speedsemiconductor device of short gate length on a Si substrate formed on aninsulation film such as a polysilicon film, and thus, it has beendifficult to realize a three-dimensional integrated circuit by stackinga number of insulation films each carrying a semiconductor device.

SUMMARY OF THE INVENTION

Accordingly, it is a general object of the present invention to providea novel and useful semiconductor device and fabrication process thereofwherein the foregoing problems are eliminated.

Another object of the present invention is to provide an insulation filmforming technology capable of forming a high-quality insulation film ona (111) surface of a Si crystal at a low temperature below about 550°C., a fabrication process of a semiconductor device on a (111) surfaceof a Si crystal by using such a insulation film forming technology, anda semiconductor device fabricated according to such a fabricationprocess.

Another object of the present invention is to provide a semiconductordevice, comprising a Si crystal having a (111) surface, and aninsulation film formed on said (111) surface of said Si crystal, atleast a part of said insulation film comprising a Si oxide filmcontaining Kr.

Another object of the present invention is to provide a semiconductordevice comprising a Si crystal having a (111) surface, and an insulationfilm formed on said (111) surface of said Si crystal, at least a part ofsaid insulation film comprising a silicon nitride film containing Ar orKr.

Another object of the present invention is to provide a semiconductorintegrated circuit device, comprising at least one metal layer, a Silayer formed above said metal layer with an insulation film interposedtherebetween, said Si layer having a (111) principal surface, and aplurality of transistors formed on said Si layer, at least a part ofsaid insulation film formed on said silicon layer comprising a Si oxidefilm containing Kr.

Another object of the present invention is to provide a semiconductorintegrated circuit, characterized by at least one metal layer, a Silayer formed above said metal layer with an insulation film interposedtherebetween, said Si layer having a (111) principal surface, and aplurality of transistors formed on said Si layer, at least a part of aninsulation film formed on said silicon layer comprising a siliconnitride film containing Ar or Kr.

According to the present invention, active atomic state oxygen O* areformed efficiently by activating O₂ in Kr plasma excited by a microwave.By causing the atomic state oxygen O* to react, it becomes possible toform a Si oxide film having a quality superior to a silicon thermaloxide film formed at about 1000° C. on the (111) surface of a Sicrystal. By using the Si oxide film thus formed as a gate insulationfilm, it becomes possible to form a high-performance semiconductordevice or a semiconductor integrated circuit device on the (111) surfaceof the Si crystal. The (111) surface of the Si crystal may be the onedefining the principal surface of the Si single crystal substrate or theone formed in a part thereof. Further, the (111) surface may be the oneappearing at the surface of a polysilicon film.

According to the present invention, active hydrogen nitride radicals NH*are formed efficiently by activating NH₃ or a mixed gas of N₂ and H₂ inmicrowave exited plasma of Ar or Kr. By causing the hydrogen nitrideradicals NH₃* to react, it becomes possible to form a silicon nitridefilm having a quality superior to a silicon thermal oxide film formed atabout 1000° C. on the (111) surface of a Si crystal at a low temperatureof 550° or less. The silicon nitride film thus formed can be used as ahigh-dielectric gate insulation film and it becomes possible to form ahigh-performance semiconductor device or a high-performancesemiconductor integrated circuit device on the (111) surface of the Sicrystal. It should be noted that the (111) surface of the Si crystal maybe the one defining the principal surface of a Si single crystalsubstrate or the one formed in a part thereof. Further, the (111)surface may be the one appearing at the surface of a polysilicon film.

According to the present invention, it becomes possible to form ahigh-quality Si oxide film or a silicon nitride film on the (111)surface formed at the corner part of the device isolation groove of anSTI structure. As a result, it becomes possible to reduce the leakagecurrent of the STI structure and the breakdown characteristic thereofwithout increasing the width of the device isolation groove. As aresult, it becomes possible to improve the electric property and thereliability in the semiconductor device that has such an STI structure.

Further, the present invention is applicable also to semiconductordevices in which requirement of high film quality and stability isimposed to gate insulation film, such as a ferroelectric memory deviceor a flash memory device.

Further, the present invention enables formation of high-quality gateoxide film or gate nitride film on a Si film formed of Si crystalspreferentially oriented in the <111> direction. Thus, it becomespossible to realize a polysilicon transistor or a thin film transistorhaving a large driving power. Further, it becomes possible to realize athree-dimensional integrated circuit device in which functional devicesare stacked in plural layers.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram schematically showing the concept of a plasmaprocessing apparatus that uses a radial line slot antenna;

FIG. 2 is a diagram showing the relationship between the thickness of anoxide film formed by the plasma processing apparatus of FIG. 1 and thepressure of the processing chamber;

FIG. 3 is a diagram showing the relationship between the thickness of anoxide film formed by the plasma processing apparatus of FIG. 1 and theoxidation time;

FIG. 4 is a diagram showing the depth profile of Kr concentration in theSi oxide film formed by the plasma processing apparatus of FIG. 1;

FIG. 5 is a diagram showing the surface state density in the Si oxidefilm formed by the plasma processing apparatus of FIG. 1;

FIG. 6 is a diagram showing the relationship between the oxygen partialpressure in the atmosphere used in the plasma processing apparatus ofFIG. 1 for forming an Si oxide film and the surface state density andbreakdown voltage of the Si oxide film thus formed;

FIG. 7 is a diagram showing the relationship between the total pressureused in the plasma processing apparatus of FIG. 1 for forming an Sioxide film and the surface state density and breakdown voltage of the Sioxide film thus formed;

FIG. 8 is a diagram showing the relationship between the total pressureof the atmosphere used in the plasma processing apparatus of FIG. 1 forforming a nitride film and the thickness of the nitride film thusformed;

FIG. 9 is a diagram showing the current-voltage characteristic of asilicon nitride film formed by the substrate processing apparatus ofFIG. 1;

FIGS. 10A-10D are diagrams showing the construction of a MOS transistoraccording to a first embodiment of the present invention;

FIGS. 11A-11C are cross-sectional diagrams showing a part of asemiconductor integrated circuit device having an STI structureaccording to a second embodiment of the present invention;

FIG. 12 is a cross-sectional diagram showing the schematic constructionof a ferroelectric memory device according to a third embodiment of thepresent invention;

FIG. 13 is a cross-sectional diagram showing the schematic constructionof a flash memory device according to a fourth embodiment of the presentinvention;

FIG. 14 is a cross-sectional diagram showing the schematic diagram of aMOS transistor formed on an SOI structure formed in turn on a metalsubstrate according to a fifth embodiment of the present invention;

FIG. 15 is a cross-sectional diagram showing the schematic constructionof a plasma processing apparatus applicable to a glass substrate orplastic substrate;

FIG. 16 is a cross-sectional diagram showing the schematic constructionof a polysilicon transistor according to a sixth embodiment of thepresent invention; and

FIG. 17 is a cross-sectional diagram showing the schematic constructionof a three-dimensional semiconductor integrated circuit according to aseventh embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[Principle]

First, low temperature oxide film formation using plasma will bedescribed.

FIG. 2 is a cross-sectional diagram showing the construction of anexemplary microwave plasma processing apparatus used in the presentinvention for realizing the oxidation process, wherein the microwaveplasma processing apparatus uses a radial line slot antenna (seeWO98/33362). The novel feature of the present embodiment is to use Kr asthe plasma excitation gas at the time of forming the oxide film.

Referring to FIG. 2, the microwave plasma processing apparatus includesa vacuum vessel (processing chamber) 101 accommodating therein a stage104 on which a substrate 103 to be processed is supported. Theprocessing chamber 101 is evacuated to a vacuum state, and a Kr gas andan O₂ gas are introduced from a shower plate 102 formed at a part of thewall of the processing chamber 101 such that the pressure inside theprocessing chamber is set to about 1 Torr (about 133 Pa). Further, adisk-shaped substrate such as a silicon wafer is placed on the stage 104as the foregoing substrate 103. The stage 104 includes a heatingmechanism, and the temperature of the substrate 103 is set to about 400°C. It is preferable to set the temperature in the range of 200-550° C.As long as the temperature is set in this range, a similar result isobtained.

Next, a microwave of 2.45 GHz is supplied from an external microwavesource via a coaxial waveguide 105 connected thereto, wherein themicrowave thus supplied is radiated into the processing chamber 101 bythe radial line slot antenna 106 through a dielectric plate 107. As aresult, there is formed high-density plasma in the processing chamber101. As long as the frequency of 900 MHz or more but not exceeding 10GHz is used for the microwave, a result similar to the one describedbelow is obtained. In the illustrated example, the distance between theshower plate 102 and the substrate 103 is set to about 6 cm. Narrowerthe distance, faster the film forming process.

While the present embodiment shows the example of forming a film byusing the plasma apparatus that uses the radial line slot antenna, it isalso possible to introduce a microwave into the processing chamber byother means.

In the high-density plasma in which an Kr gas and an O₂ gas are mixed,Kr* at the intermediate excitation state cause collision with the O₂molecules and there occurs efficient formation of atomic state oxygenO*, and the atomic state oxygen O* thus formed cause oxidation of thesubstrate surface. It should be noted that oxidation of a siliconsurface has conventionally been conducted by using H₂O or O₂ moleculesat very high process temperature such as 800° C. or more. In the case ofusing atomic state oxygen, on the other hand, it becomes possible tocarry out the oxidation process at a low temperature of 550° C. or less.

In order to increase the chance of collision between K* and O₂, it ispreferable to increase the pressure in the processing chamber 101. Onthe other hand, the use of too high pressure in the processing chamberincreases the chance that O* causing collision with another O* andreturning to the O₂ molecule. Thus, there would exist an optimum gaspressure.

FIG. 2 shows the thickness of the oxide film for the case in which thetotal pressure inside the processing chamber 101 is changed whilemaintaining the Kr and oxygen pressure ration such that the proportionof Kr is 97% and the proportion of oxygen is 3%. In the experiment ofFIG. 2, it should be noted that the silicon substrate was held at 400°C. and the oxidation was conducted over the duration of 10 minutes.

Referring to FIG. 2, it can be seen that the thickness of the oxide filmbecomes maximum when the total gas pressure in the processing chamber101 is set to 1 Torr, indicating that the oxidation process becomesoptimum under this pressure or in the vicinity of this pressure.Further, it should be noted that this optimum pressure remains the samein the case the silicon substrate has the (100) oriented surface andfurther in the case the silicon substrate has the (111) orientedsurface.

FIG. 3 shows the relationship between the thickness of the oxide filmand the duration of the oxidation processing for the oxide film that isformed by oxidation of the silicon substrate surface using the Kr/O₂high-density plasma. In FIG. 3, the result for the case in which thesilicon substrate has the (100) oriented surface and the result for thecase in which the silicon substrate has the (111) oriented surface areboth represented. Further, FIG. 3 also represents the oxidation timedependence for the case a conventional dry oxidation process at thetemperature of 900° C. is employed.

Referring to FIG. 3, it can be seen that the oxidation rate caused bythe Kr/O₂ high-density plasma oxidation processing, conducted at thetemperature of 400° C. under the chamber pressure of 1 Torr, is largerthan the oxidation rate of a dry O₂ process conducted at 900° C. underthe atmospheric pressure.

From FIGS. 2 and 3, it can be seen that the productivity of theoxidation processing of the substrate surface is improved substantiallyby conducting oxidation of the silicon substrate surface by using theKr/O₂ high-density plasma. In the conventional high-temperature thermaloxidation process, it should be noted that the O₂ molecules or H₂Omolecules in the atmosphere have to penetrate through the oxide film onthe surface by diffusion in order that the O₂ molecules or the H₂Omolecules reach the silicon/Si oxide interface and cause an oxidationtherein. Thus, the oxidation rate of the substrate surface has beencontrolled by the diffusion rate of the O₂ or H₂O molecules through theoxide film. Because of this reason, it has been commonly accepted thatthe thickness of an oxide film would increase with time t according tothe function of t^(1/2). In the Kr/O₂ high-density plasma oxidationprocess of the present invention, on the other hand, it is noted that aconstant oxidation rate is maintained up to the point in which thethickness of the oxide film reaches 35 nm and the oxide thicknessincreases linearly with time. This indicates that the atomic stateoxygen O* have a very large diffusion rate in the Si oxide film and theatomic state oxygen O* can pass through the Si oxide film freely.

With regard to orientation dependence of oxide film thickness, theresult of FIG. 3 indicates that, in the case of conventional dry thermaloxidation process at 900° C., the growth rate of the oxidation film islarger when the oxide film is formed on the (111) oriented siliconsurface as compared with the case of forming the oxide film on the (100)oriented silicon surface. In the case in which the Kr/O₂ high-densityplasma oxidation process is used, on the other hand, this relationshipis reversed and the growth rate of the oxide film on the (111) surfacebecomes smaller than the growth rate of the oxide film on the (100)surface.

In view of the fact that silicon atoms are arranged in a Si substratewith larger surface density on the (111) oriented surface than on the(100) oriented surface, it is predicted that the oxidation rate shouldbe smaller on the (111) surface than on the (100) surface as long as thesupply rate of the oxygen radicals is the same. The result of theforegoing oxidation process of the silicon substrate surface is in goodconformity with this prediction when the Kr/O₂ high-density plasma isused for the oxidation process, indicating that there is formed a denseoxide film similar to the one formed on a (100) surface, also on the(111) surface. In the conventional case, on the other hand, theoxidation rate of the (111) surface is much larger than the oxidationrate of the (100) surface. This indicates that the oxide film formed onthe (111) film would be sparse in the film quality as compared with theoxide film formed on the (100) surface.

FIG. 4 shows the depth profile of the Kr density inside the siliconoxide film that is formed according to the foregoing process, whereinthe depth profile FIG. 4 was obtained by a total-reflection fluorescentX-ray spectrometer. In the experiment of FIG. 4, the formation of thesilicon oxide film was conducted at the substrate temperature of 400° C.while setting the oxygen partial pressure in the Kr gas to 3% andsetting the pressure of the processing chamber to 1 Torr (about 133 Pa).

Referring to FIG. 4, it can be seen that the Kr density in the oxidefilm decreases with decrease of the film thickness and reaches a valueof about 2×10¹¹ cm⁻² is at the surface of the silicon oxide film. Thus,the silicon oxide film thus formed has a uniform Kr concentration levelin the film when the thickness is 4 nm or more. Further, the Krconcentration level decreases toward the silicon/Si oxide interface.

FIG. 5 shows the surface state density of the oxide film thus formed,wherein the result of FIG. 5 was obtained by a low-frequency C-Vmeasurement. The silicon oxide film was formed at the substratetemperature of 400° C. while using the apparatus of FIG. 1. In theexperiment, the oxygen partial pressure in the rare gas was set to 3%and the pressure in the processing chamber was set to 1 Torr. For thesake of comparison, the surface state density of a thermal oxide filmformed at 900° C. in a 100% O₂ atmosphere is also represented.

Referring to FIG. 5, it can be seen that the surface state density ofthe oxide film is small in both of the cases in which the oxide film isformed on the (100) surface and in which the oxide film is formed on the(111) surface as long as the oxide film is formed in the Kr plasma. Thevalue of the surface state density thus achieved is comparable with thesurface state density of a thermal oxide film formed on the (100)surface in a dry oxidation atmosphere at 900° C. Contrary to theforegoing, the thermal oxide film formed on the (111) surface has asurface state density much larger than the foregoing surface statedensity by a factor of ten.

The mechanism of the foregoing results may be the one described below.

Viewing a Si crystal surface from the side of an silicon oxide filmduring an oxidation process of the Si crystal, there appear two bondsfor one silicon atom when the silicon surface is a (100) surface. On theother hand, there appear one bond and three bonds alternately for onesilicon atom when the silicon surface is a (111) surface.

Thus, when a conventional thermal oxidation process is applied to a(111) surface, oxygen atoms quickly cause bonding to all the foregoingthree bonds, leaving the remaining bond behind the silicon atomun-bonded. Thereby, the remaining bond may extend and form a weak bondor disconnected and form a dangling bond. When this is the case, thereinevitably occurs an increase of surface state density. When thehigh-density plasma oxidation is conducted in the mixed gas of Kr andO₂, Kr* of the intermediate excitation state cause collision with O₂molecules and there occurs efficient formation of atomic state oxygenO*, wherein the atomic state oxygen O* thus formed easily reach the weakbond or dangling bond noted before and form a new silicon-oxygen bond.With this, it is believed that the surface states are reduced also onthe (111) surface.

FIG. 6 shows a relationship between the O₂ partial pressure used in thesubstrate processing apparatus of FIG. 1 for forming the silicon oxidefilm and the breakdown voltage of the silicon oxide film thus formed.Further, FIG. 6 shows the relationship between the O₂ partial pressureand the surface state density of the silicon oxide film. In theexperiment of FIG. 6, the pressure inside the processing chamber is setto 1 Torr. A similar relationship is obtained in the case the Si oxidefilm is formed on the (100) surface and in the case the silicon oxidefilm is formed on the (111) surface.

Referring to FIG. 6, it can be seen that the surface state density inthe oxide film becomes minimum when the O₂ partial pressure is 3%, and asurface state density equivalent to the surface state density of athermal oxide film is obtained. Further, it can be seen that thebreakdown voltage of the Si oxide film becomes maximum in the vicinityof the oxygen partial pressure of 3%. From this, it is concluded thatthe oxygen partial pressure is preferably set to 2-4% when conducting alow-temperature plasma oxidation process by using the Kr/O₂ mixed gas.

FIG. 7 shows a relationship between the process pressure used whenforming a silicon oxide film by the low-temperature plasma oxidationprocessing in the Kr/O₂ mixed gas and the breakdown voltage of thesilicon oxide film thus formed. Further, FIG. 7 shows the relationshipbetween the process pressure and the surface state density of thesilicon oxide film. In FIG. 7, it should be noted that the oxygenpartial pressure is set to 3%. Further, it should be noted that asimilar relationship is obtained also in the case the Si oxide film isformed on the (100) surface and on the (111) surface.

Referring to FIG. 7, it can be seen that the breakdown voltage of thesilicon oxide film becomes maximum and the surface state density becomesminimum when the process pressure of about 1 Torr is used at the time ofthe oxide film formation. From the result of this, it is concluded thatthe preferable pressure of forming an oxide film by using a Kr/O₂ mixedgas would be in the rage of 800-1200 mTorr.

In addition to the foregoing, other various preferable features wereobtained for the oxide film formed by the Kr/O₂ high-density plasmaprocess with regard to electronic and reliability characteristics,including breakdown characteristics, leakage characteristics, hotcarrierresistance, and the QBD (Charge-to-Breakdown) characteristics, whereinthe QBD represents the amount of electric charges that leads a siliconoxide film to breakdown as a result of application of a stress current.The characteristics thus obtained are comparable to those of the thermaloxide film that is formed at 900° C.

As noted above, the oxide film formed by the Kr/O₂ high-density plasmashows excellent characteristics equivalent to those of a conventionalhigh-temperature thermal oxide film formed on the (100) surface,irrespective of whether the oxide film is formed by the oxidation of the(100) surface or the oxide film is formed by the oxidation of the (111)surface, in spite of the fact that the oxide film is formed by theoxidation process at low temperature of 400° C. One reason such apreferable result is obtained may be that the oxide film thus formedcontains Kr therein.

In more detail, the Kr atoms thus incorporated into the oxide film isthought as causing relaxation of stress in the film or in the Si/SiO₂interface. The relaxation of stress thus achieved, in turn, may resultin a reduction of trapping electric charges or surface state density,while such a reduction of the defects leads to the observed improvementof the electric properties of the Si oxide film. Particularly, it isthought important that the Si oxide film contains therein Kr with asurface density of 5×10¹¹ cm⁻² for improving the electric properties andreliability properties of the Si oxide film as represented in FIG. 4.

By using the gate oxide film, a MIS transistor is formed and thesurface-orientation dependence of the channel mobility is measured. As aresult, it was confirmed, as will be explained later with reference toembodiment, that there occurs an increase of channel mobility by thefactor of about 1.2 or more when the transistor is formed on the Si(111) surface as compared with the case of forming the transistor on theSi (100) surface, for both of the cases in which the MIS transistor is ap-channel transistor and the MIS transistor is an n-channel transistor.

It should be noted that the process of the oxide film formation of thepresent invention is by no means limited to the one that uses thesubstrate processing apparatus of FIG. 1, but any other plasmaprocessing apparatuses may be used, as long as low-temperature oxidefilm formation is possible by a plasma process. For example, it ispossible to use a two-stage shower-plate type plasma processingapparatus that uses first gas releasing means that releases a Kr gas forcausing microwave excitation of plasma and a second gas releasing meansthat releases an oxygen gas.

Next, a low-temperature nitride film formation conducted by using plasmawill be explained.

The nitride film formation of the present invention is conducted also bythe substrate processing apparatus of FIG. 1, wherein it should be notedAr or Kr is used as the plasma excitation gas at the time of the nitridefilm formation.

Thus, the vacuum vessel (processing chamber) 101 is evacuated to a highvacuum state first, and the pressure inside the processing chamber 101is then set to about 100 mTorr (about 13 Pa) by introducing an Ar gasand a NH₃ gas via the shower plate 102. Further, a disk-shaped substratesuch as a silicon wafer is placed on the stage 104 as the substrate 103and the substrate temperature is set to about 500° C. As long as thesubstrate temperature is in the range of 400-500° C., almost the sameresults are obtained.

Next, a microwave of 2.45 GHz is introduced into the processing chamberfrom the coaxial waveguide 105 via the radial line slot antenna 106 andfurther through the dielectric plate 107, and there is inducedhigh-density plasma in the processing chamber. It should be noted that asimilar result is obtained as long as a microwave in the frequency of900 MHz or more but not exceeding 10 GHz is used. In the illustratedexample, the distance between the shower plate 102 and the substrate 103is set to 6 cm. Narrower the distance, faster the film formation rate.

While the present embodiment shows the example of forming a film byusing the plasma apparatus that uses the radial line slot antenna, it ispossible to use other method for introducing the microwave into theprocessing chamber. In the present embodiment, it should be noted thatan Ar gas is used for exciting plasma. However, a similar result isobtained also when a Kr gas is used. While the present embodiment usesNH₃ for the plasma process gas, it is also possible to use a mixed gasof N2 and H2 for this purpose.

In the high-density plasma excited in the mixed gas of Ar or Kr and NH₃(or alternatively N₂ and H₂), there are formed NH* radicals efficientlyby Ar* or Kr* having an intermediate excitation state, and the NH*radicals thus formed cause the desired nitridation of the substratesurface.

Conventionally, there has been no report of direct nitridation ofsilicon surface. Thus, a nitride film has been formed by a plasma CVDprocess, and the like. However, the nitride film thus formed by aconventional plasma CVD process does not have the quality required for agate insulation film of a transistor. In the nitridation process ofsilicon according to the present embodiment, on the other hand, it ispossible to form a high-quality nitride film at low temperature on anyof the (100) surface and the (111) surface, irrespective of the surfaceorientation of the silicon substrate.

Meanwhile, it should be noted that existence of hydrogen is an importantfactor when forming a silicon nitride film by the process of the presentinvention. With the existence of hydrogen in plasma, the dangling bondsexisting in the silicon nitride film or at the nitride film interfaceare terminated in the form of Si—H bond or N—H bond, and the problem ofelectron trapping within the silicon nitride film or on the siliconnitride interface is eliminated.

The existence of the Si—H bond and the N—H bond in the nitride film isconfirmed in the present invention by infrared absorption spectroscopyor X-ray photoelectron spectroscopy. As a result of the existence ofhydrogen, the hysteresis of the CV characteristic is also eliminated,and the surface state density of the silicon/silicon nitride interfaceis suppressed to the level of below 3×10¹⁰ cm⁻². When forming thesilicon nitride film by using a rare gas (Ar or Kr) and a mixed gas ofN₂/H₂, it becomes possible to reduce the trapping of electrons or holesin the film sharply by setting the H₂ partial pressure in the mixed gasto be 0.5% or more.

FIG. 8 shows the pressure dependence of the film thickness of thesilicon nitride film thus formed according to the foregoing process. Inthe illustrated example, the ratio of the Ar gas to the NH₃ gas is setto 98:2 in terms of partial pressure, and the film formation wasconducted over the duration of 30 minutes.

Referring to FIG. 8, it can be seen that the growth rate of the nitridefilm increases when the pressure in the processing chamber 101 isreduced so as to increase the energy given to NH₃ (or N₂/H₂) from theinert gas (Ar or Kr). From the viewpoint of efficiency of nitridation,it is therefore preferable to use the gas pressure of 50-100 mTorr(about 7-13 Pa). Further, it is preferable to set the partial pressureof NH₃ (or N₂/H₂) in the rare gas atmosphere to 1-10%, more preferablyto 2-6%.

It should be noted that the silicon nitride film of the presentembodiment has a dielectric constant of 7.9, which is almost twice aslarge as that of a silicon oxide film.

FIG. 9 shows the current-voltage characteristic of the silicon nitridefilm of the present embodiment. It should be noted that the result ofFIG. 9 is obtained for the case in which a silicon nitride film having athickness of 4.2 nm (2.1 nm in terms of oxide film equivalent thickness)is formed by using a gas mixture of Ar/N₂/H₂ while setting the gascomposition ratio, Ar:N₂:H₂, to 93:5:2 in terms of partial pressure. InFIG. 9, the result for the foregoing nitride film is compared also withthe case of a thermal oxide film having a thickness of 2.1 nm.

Referring to FIG. 9, it can be seen that there is realized a very smallleakage current, smaller than the leakage current of a silicon oxidefilm by a factor of 10⁴ or more, for the Si nitride film, provided thata voltage of 1 V is applied thereto for the measurement. This result ofFIG. 9 indicates that there is a possibility of breaking through thelimitation hitherto imposed on miniaturization of transistors due to theleakage current in the gate oxide film, by using the Si nitride film ofthe present invention.

It should be noted that the foregoing condition of film formation, theproperty of the film, or the electric characteristic of the film areobtained similarly on any of the surfaces of the silicon crystal. Inother words, the same result is obtained on the (100) surface and alsoon the (111) surface.

It should be noted that the existence of the Si—H bond or N—H bond inthe film is not the only cause of the foregoing advantageous feature ofthe present invention of realizing a nitride film having a leakagecurrent characteristic superior to that of a thermal oxide film on a Si(100) surface. The existence of Ar or Kr in the film contributes also tothe foregoing advantageous result. As a result of the existence of Ar orKr in the film, it should be noted that the stress within the nitridefilm or the stress at the silicon/nitride film interface is relaxedsubstantially, while this relaxation of stress also contributes to thereduction of fixed electric charges and the surface state density in thesilicon nitride film, which leads to the remarkable improvement ofelectric properties and reliability. Particularly, the existence of Aror Kr with the surface density of 5×10¹¹ cm⁻² or less at the filmsurface is thought as contributing effectively to the improvement ofelectric characteristics and reliability of the silicon nitride film,just in the case of the silicon oxide film represented in FIG. 4.

By using the nitride film of the present invention for the gateinsulation film, a MIS transistor is formed and the surface-orientationdependence of the channel mobility is measured. As a result, it wasconfirmed, as will be explained later with reference to embodiment, thatthere occurs an increase of channel mobility by the factor of about 1.3or more when the transistor is formed on the Si (111) surface ascompared with the case of forming the transistor on the Si (100)surface, for both of the cases in which the MIS transistor is ap-channel transistor and the MIS transistor is an n-channel transistor.

It should be noted that the process of the nitride film formation of thepresent invention is by no means limited to the one that uses thesubstrate processing apparatus of FIG. 1, but any other plasmaprocessing apparatuses may be used, as long as low-temperature oxidefilm formation is possible by a plasma process. For example, it ispossible to use a two-stage shower-plate type plasma processingapparatus that uses first gas releasing means that releases an Ar or Krgas for causing microwave excitation of plasma and second gas releasingmeans that releases an NH₃ gas (or a mixed gas of N₂ and H₂)

[First Embodiment]

Next, a description will be made on a semiconductor device according toa first embodiment of the present invention that uses a two-layerstructure of low-temperature oxide film and nitride film formed in aplasma for the gate insulation film.

In the present embodiment, the substrate processing apparatus of FIG. 1is used for the formation of the oxide film and nitride film. Thereby,Kr is used for the plasma gas.

Referring to FIG. 1, the vacuum vessel (processing chamber) 101 isevacuated to a vacuum state and a Kr gas and an O₂ gas are introducedinto the processing chamber 102 from the shower plate 102 such that thepressure inside the processing chamber 101 is set to about 1 Torr.Further, the temperature of the silicon wafer is set to about 450° C.

Next, a microwave having the frequency of 2.45 GHz is introduced intothe processing chamber from the coaxial waveguide 105 through the radialline slot antenna 106 and the dielectric plate 107, and high-densityplasma is formed in the processing chamber 101. As a result, a Si oxidefilm is formed on the Si substrate constituting the wafer with athickness of about 1 nm.

Next, the supply of the microwave is interrupted temporally, and thesupply of the Kr gas and the O₂ gas is interrupted. Further, theprocessing chamber 101 is evacuated to high vacuum state. Next, a Kr gasand an NH₃ gas is introduced from the shower plate 102, and the pressureinside the processing chamber 101 is set to about 100 mTorr. Further,the microwave of the 2.45 GHz frequency is introduced again into theprocessing chamber 101 to form high-density plasma therein. As a result,a Si nitride film is formed on the Si oxide film with a thickness ofabout 2 nm.

The stacked film of the Si oxide film and the Si nitride film thusformed is characterized by a very small surface state density asexplained with reference to FIG. 5, and the stacked film as a whole hasan effective specific dielectric constant of about 6.7. Further, it wasconfirmed that the stacked film thus formed shows excellent electric andreliability performance in terms of leakage current characteristics,breakdown characteristics, hotcarrier resistance, and the like. Thestacked film shows no dependence of surface orientation, and the filmformed on the (100) surface and the film formed on the (111) surfaceboth have excellent performance.

FIGS. 10A-10D show the fabrication process of a MIS transistor accordingto a first embodiment of the present invention.

Referring to FIG. 10A, a stacked gate insulation film 12 is formed on a(100) principal surface or a (111) principal surface of a Si substrate11, by depositing a Si oxide film 12A and a Si nitride film 12B withrespective thicknesses of 1 nm and 2 nm by conducting the process stepsexplained before in the substrate processing apparatus of FIG. 1. Next,in the step of FIG. 10B, a polysilicon film 13 is deposited on thestacked gate insulation film 12.

Next, in the step of FIG. 10C, the polysilicon film 13 is patterned intoa gate electrode 13A, and ion implantation process of impurity elementis conducted into the Si substrate 11 while using the gate electrode 13Aas a mask. As a result, LDD regions 11A and 11B are formed in thesubstrate 11 at both lateral sides of the gate electrode 13A.

Next, in the step of FIG. 10D, sidewall insulation films 14A and 14B areformed on respective sidewall surfaces of the gate electrode 13A, andhigh-concentration diffusion regions 11C and 11D are formed in thesubstrate 11 at outer regions of the sidewall insulation films 14A and14B as source and drain regions of the MIS transistor. The diffusionregions 11C and 11D are formed by conducting an ion implantation processof an impurity element while using the sidewall insulation films 14A and14B as a mask.

According to the MIS transistor of the present invention, the gateinsulation film 12 has the nature of low surface state densitycharacteristic to an oxide film and the nature of high dielectricconstant characteristic to a nitride film, and it becomes possible tosuppress the increase of the gate leakage current even in the case thegate length Lg is reduced below 0.1 μm.

Measurement of the channel mobility conducted on the MIS transistor ofFIG. 10D with regard to the surface orientation dependence of thechannel mobility has revealed the fact that the channel mobilityincreases by the factor of about 1.2 or more in the transistor formed onthe (111)-oriented Si substrate as compared with the transistor formedon the (100)-oriented Si substrate, irrespective of whether the MIStransistor is an n-channel transistor or the MIS transistor is ap-channel transistor.

In the present embodiment, the stacked gate insulation film 12 includesthe oxide film 12A at the side of the Si substrate 11. However, it isalso possible to reverse the order of the oxide film 12A and the nitridefilm 12B according to the needs. Further, it is possible to use astacked gate insulation film in which further layers are stacked, suchas the one having an oxide/nitride/oxide structure or anitride/oxide/nitride structure in place of the stacked gate insulationfilm 12.

[Second Embodiment]

FIG. 11A shows a typical conventional STI structure.

Referring to FIG. 11A, the STI structure is formed by the steps offorming a device isolation groove by applying a plasma etching processto the surface of a Si substrate 1003, depositing a Si oxide film 1002on the surface of the Si substrate 1003 thus formed with the deviceisolation groove by a CVD process, and planarizing the Si oxide film1002 thus deposited by a CMP process, and the like, to remove the Sioxide film from the surface of the Si substrate 1003.

After the foregoing polishing step by the CMP process, the exposed Sisubstrate surface is subjected to a sacrificing oxidation process at800-900° C., and the Si oxide film formed as a result of the sacrificingoxidation process is etched by an agent containing HF. Thereby, a highlyclean Si substrate is obtained.

The clean substrate surface thus obtained is further cleaned by using anRCA cleaning process, and the like, and a gate insulation film 1001 isformed on the Si substrate surface with a thickness of about 4 nm.

In such a conventional STI structure, there has been a problem, when agate insulation film is formed on the Si substrate having the (100)surface orientation by a thermal oxidation process, in that thethickness of the Si oxide film is reduced at a corner part 1004 of thedevice isolation groove as represented in FIG. 11B, irrespective ofwhether the Si oxide film is formed by a dry oxidation process or a wetoxidation process, or irrespective of the temperature of the filmformation. It should be noted that an (111) surface of Si is exposed atsuch a corner part. Thus, such a conventional STI structure has causedthe problem of increase of leakage current in such a corner part 1004,and the semiconductor device or semiconductor integrated circuit devicehas suffered from the problem of unstable operational characteristic.

In the case, a Si oxide film is formed according to the Kr/O₂ plasmaoxidation process explained before, it was confirmed that there occursno thinning of the Si oxide film such as the one represented in FIG.11B. See the corner part 1705 of the device isolation groove representedin FIG. 11C. It is believed that the result of FIG. 11C is the outcomeof the atomic state oxygen O* reaching the region in the vicinity of thecorner part 1005 efficiently in the Kr/O₂ plasma oxidation processing ofthe present invention.

The overall QBD (Charge-to-Breakdown) characteristic of the STIstructure thus formed by the Kr/O₂ plasma oxidation processing isexcellent and it was confirmed that no breakdown occurs until theinjected electric charges reach a value of 102 C/cm². Thereby, thereliability of the semiconductor integrated circuit device is improvedsubstantially.

In the case the Si oxide film in the STI structure is formed byconventional thermal oxidation process, the degree of thinning of the Sioxide film at the foregoing corner part increases with increasing taperangle of the device isolation groove. However, no such a thinning of theoxide film occurs when the oxide film is formed by the Kr/O₂ plasmaoxidation processing of the present invention, even when the taper angleof the device isolation groove is increased. Thus, the present inventionenables use of a device isolation groove having a steep taper angle inan STI structure. As a result, it becomes possible to reduce the areaoccupied by an STI structure on a substrate. Thus, the present inventionenables further improvement of integration density of semiconductorintegrated circuits. Conventionally, the taper angle of the deviceisolation groove has been set to about 70 degrees because of the reasonsnoted before. On the contrary, excellent characteristics are obtainedeven when the taper angle of 90 degrees is used. Thus, it becomespossible to achieve an integration density twice as large as that of aconventional semiconductor integrated circuit.

In the case a Si nitride film is formed on the (100) principal surfaceof the Si substrate by the Ar/NH₃ plasma nitriding processing, it isalso possible to form a Si nitride film on the corner part 1001 of thedevice isolation groove where the (111)-oriented surface is exposed,with high film quality and without localized thinning of the filmthickness. As a result, the semiconductor integrated circuit having suchan STI structure shows excellent electric characteristics and highreliability. Similarly to the case of oxidation process, the behavior ofradicals is important in the plasma nitriding process. It is believedthat the NH* radicals thus formed are transported efficiently to thecorner part 1001 of FIG. 11A, particularly to the region in the vicinityof the corner part 1005 of FIG. 11C.

In the construction of FIG. 11A, a MIS transistor is formed by providinga Si nitride film having a thickness of 4 nm (Si oxide equivalentthickness of 2 nm) as the gate insulation film 1001. It was observedthat the MIS transistor thus formed has excellent electric properties,particularly with regard to the driving power, which has a value twiceas large as that of a MIS transistor having a Si oxide film of 4 nmthickness as the gate insulation film.

[Third Embodiment]

FIG. 12 is a cross-sectional diagram showing the schematic constructionof a ferroelectric memory device according to a third embodiment of thepresent invention.

Referring to FIG. 12, the ferroelectric memory device is constructed ona Si substrate in which a p-type well 1101 is formed, wherein the p-typewell 1101 is formed with a source region 1102 and a drain region 1102′of n-type. Further, a Si nitride film 1103 is formed on the Si substratewith a thickness of 5 nm as the gate insulation film, wherein thenitride film 1103 is formed by the foregoing Ar/NH₃ plasma processingconducted at the temperature of 400° C. Further, a polysilicon gateelectrode 1104 of n-type is formed on the gate insulation film 1103.

Further, a Si nitride film 1105 is formed on the polysilicon gateelectrode 1104 with a thickness of 5 nm by conducting the foregoingAr/NH₃ plasma nitriding processing at the temperature of 400° C., and aferroelectric film 1106 of SrTaNbO system is formed on the Si nitridefilm 1105 with a thickness of about 150 nm. Further, a Pt electrode 1107is formed on the ferroelectric film 1106.

Typically, the ferroelectric film 1106 is formed by a sputtering processsuch that there appears a Sr:Ta:Nb of 1:0.7:0.3 in the ferroelectricfilm, and a plasma oxidation process is conducted thereafter at thetemperature of 400° C. by carrying out the Kr/O₂ plasma oxidationprocessing explained before. As a result, the ferroelectric film 1106has a composition represented as Sr₂(Ta_(0.7)Nb_(0.3))₂O₇.

It should be noted that the source region 1102 and the drain region1102′ are formed by conducting an ion implantation without causing theions to pass through the gate oxide film, and an electric activationprocess is conducted thereafter at 400° C. The ferroelectric memorydevice of FIG. 12 uses a gate length of 0.35 μm.

The ferroelectric film of the SrTaNbO system has a specific dielectricconstant of about 40 and has been known as being effective for reducingthe writing voltage of a ferroelectric memory device that uses a thermaloxide film for the gate insulation film. The present invention uses, onthe contrary, a silicon nitride film formed by the Ar/NH₃ plasmanitriding process of the present invention for the gate insulation film1103, wherein the use of such a silicon nitride film for the gateinsulation film has become possible for the first time by the presentinvention. As a result of use of the silicon nitride film for the gateinsulation film, the dielectric constant of the gate insulation film hasincreased twice as compared with the case in which a Si oxide film isused for the gate insulation film. As a result, it becomes possible toreduce the writing voltage by a factor of about 1/1.9 in theferroelectric memory device of the present invention as compared with aconventional ferroelectric memory device.

In conventional ferroelectric memory devices, it has been practiced toprovide a diffusion barrier layer of IrO₂, and the like, between thepolysilicon gate electrode 1104 and the ferroelectric film 1106 of theSrTaNbO system. However, such a construction has a drawback in that theIr atoms in the IrO₂ film may penetrate into the underlying polysilicongate electrode 1104 and provide adversary effect to the electricproperties of the ferroelectric memory device. In the present invention,on the other hand, it has became possible to form the Si nitride film1105 on the polysilicon gate electrode 1104, which has the <111>preferred orientation, at low temperature. The Si nitride film thusformed is dense and provides no adversary effect at all to theunderlying semiconductor device. Further, the Si nitride film thusformed functions as an effective diffusion barrier film.

In conventional ferroelectric memory devices, the ferroelectric film1106 of the SrTaNbO system has been formed by a sol-gel process,followed by a crystallization process conducted by a thermal annealingprocess at high temperature of 900° C. or more. However, theferroelectric film formed by such a conventional process has sufferedfrom the problem of inhomogeneous film composition and deterioration ofdevice performance that is caused by elemental diffusion associated withthe use of high temperature. Further, the ferroelectric film thus formedshows a poor leakage characteristic. On the contrary, the presentinvention enables formation of a high-quality Sr₂(Ta_(0.7)Nb_(0.3))₂O₇film characterized by the features of excellent uniformity, free fromelement diffusion, excellent leakage current characteristic, and thelike, by accurately controlling the Sr:Ta:Nb ratio to 1:0.7:0.3 in thesputtering process of the SrTaNbO film and further by applying the Kr/O₂plasma oxidation process at low temperature.

In a ferroelectric memory integrated circuit that includes atwo-dimensional array of the ferroelectric memory devices, the writingvoltage is reduced by one-half as compared with a conventionalferroelectric memory integrated circuit device and the driving power isimproved by twice. Further, the retention time for retaining writteninformation is increased by about 100 times as compared with aconventional ferroelectric memory device. Further, the number ofpossible rewriting cycles is increased.

It should be noted that the entire process steps for forming theferroelectric memory device of the present embodiment can be conductedat a temperature of 400° C. or less. As a result, it is possible to formthe ferroelectric memory device on an SOI substrate that includes ametal layer in a Si substrate, or on a polysilicon layer formed on aninsulation layer that covers a metal interconnection pattern formed on asubstrate.

[Fourth Embodiment]

FIG. 13 is a cross-sectional diagram showing the schematic constructionof a flash memory device according to a fourth embodiment of the presentinvention.

Referring to FIG. 13, the flash memory device is formed on a Sisubstrate in which a p-type well 1201 is formed, wherein diffusionregions 1202 and 1202′ of n-type are formed in the p-type well 1201 assource and drain regions respectively.

On the Si substrate, a Si nitride film 1203 is formed by the Ar/NH₃plasma nitriding process explained before at the temperature of 400° C.with a thickness of about 6 nm, and a polysilicon floating gateelectrode 1204 is formed on the Si nitride film 1203. Further, a Sinitride film 1205 is formed on the polysilicon floating gate electrode1204 by the Ar/NH₃ plasma nitriding processing explained before at thetemperature of 400° C. with the thickness of 4 nm. Further, a controlgate electrode 1206 of polysilicon is formed on the Si nitride film1205.

During the fabrication process of the flash memory device of FIG. 13,the source region 1202 and the drain region 1202′ are formed by an ionimplantation of an n-type impurity element such that the ions areintroduced without passing through the gate oxide film. The ions thusintroduced are then activated electrically by a thermal processing at400° C. In the illustrated example, the flash memory device is formed tohave a gate length of 0.25 μm.

In the present embodiment, it becomes possible to form a low-temperaturenitride film as the gate insulation film 1203 and the insulation film1205 that covers the polysilicon gate electrode 1204 in which the <111>preferred orientation is formed. The Si nitride films 1203 and 1205 aredense and characterized by very low leakage current. As a result, theflash memory device provides a memory retention time larger by a factorof ten or more with regard to a conventional flash memory device.

It should be noted that the Si nitride film 1203 has excellenthot-carrier resistance and it becomes possible to increase the number ofrewriting cycles by a factor of ten or more as compared with aconventional flash memory device. Further, the Si nitride film 1205interposed between the floating gate electrode 1204 and the control gateelectrode 1205 maintains the excellent electrical properties even whenthe thickness thereof is reduced. Thus, it becomes possible to reducethe writing voltage significantly in the flash memory device of thepresent embodiment.

It should be noted that a flash memory integrated circuit in which theflash memory devices of the present embodiment are arranged to form atwo-dimensional array, the writing voltage is reduced by a factor ofabout 1/1.3 as compared with a conventional flash memory integratedcircuit and the writing speed is improved by twice. Further, theretention time of written information is improved by a factor of 100 ormore, and the number of rewiring cycles is increased significantly.

It should be noted that entire processes of the flash memory device ofthe present embodiment can be conducted at a temperature of about 400°C. or less. Thus, it becomes possible in the present embodiment to forma flash memory device on an SOI substrate, in which a metal layer isincluded in a Si substrate. Further, it becomes possible in the presentembodiment to form a flash memory device on a polysilicon layer that isformed on an insulation film covering a metal interconnection pattern ona substrate.

In the present embodiment, too, it becomes possible to form theinsulation films 1203 and 1205 by the Si oxide film that is formed bythe Kr/O₂ plasma oxidation process explained before.

[Fifth Embodiment]

The foregoing gate oxidation process achieved by the Kr/O₂microwave-excited high-density plasma in the substrate processingapparatus of FIG. 1, or the gate nitriding process achieved by the Ar(or Kr)/NH₃ (or N₂/H₂) microwave-excited plasma in the substrateprocessing apparatus of FIG. 1, is suitable for forming an integratedcircuit device on a metal-substrate SOI wafer. Particularly, the presentinvention is most suitable for forming a semiconductor layer on ametal-substrate SOI wafer such that the (111) surface of Si crystalforms a principal surface and for forming an integrated circuit on the(111) surface. As explained before, a high surface density is realizedfor the Si atoms in the (111) surface of a Si crystal, and thus, atransistor formed on such a (111) surface has an advantageous feature oflarge driving power.

FIG. 14 is a cross-sectional diagram showing the construction of a MOStransistor formed on a metal-substrate SOI structure.

Referring to FIG. 14, the metal-substrate SOI structure is formed of alow-resistance semiconductor layer 1301 of n+-type or p+-type, asilicide layer 1302 of NiSi, and the like, formed on the semiconductorlayer 1301, a conductive nitride layer 1303 of TaN or TiN formed on thesilicide layer 1302, a metal layer 1304 of Cu, and the like, formed onthe conductive nitride layer 1303, a conductive nitride layer 1305 ofTaN or TiN formed on the metal layer 1304, a low-resistancesemiconductor layer 1306 of n+-type or p+-type formed on the conductivenitride layer 1305, and a nitride insulation film 1307 of AlN or Si₃N₄formed on the low-resistance semiconductor layer 13306, and Si-layerregions 1314 and 1315 are formed on the nitride insulation film 1307with a separation from each other as the active region of the MOStransistor. The Si layer regions 1314 and 1315 have a (111) principalsurface.

In the Si-layer region 1314, a drain region 1310 of n+-type and a sourceregion 1311 of n+-type are formed with a mutual separation, with achannel region formed therebetween. Similarly, a drain region 1312 ofp+-type and a source region 1313 of p+-type are formed in the Si-layerregion 1315 with a channel region interposed therebetween.

Each channel region of the Si-layer regions 1314 and 1315 is covered bya gate insulation film 1316 of SiO2, wherein the gate insulation film1316 is formed by a Kr/O₂ plasma oxidation process.

In the Si-layer region 1314, an n-MOS gate electrode 1317 of Ta, Ti,TaN/Ta, TiN/Ta, and the like, is formed on the SiO₂ gate insulation film1316. Further, a p-MOS gate electrode 1318 of Ta, Ti, TaN/Ta, or TiN/Tais formed on the SiO2 gate insulation film 1316 in the Si-layer region1315.

Further, an SiO₂ film 1308 is formed on the nitride insulation film 1307so as to fill the region between the Si-layer regions 1314 and 1315, andan insulation film 1309 is formed on the SiO₂ film 1308, wherein theinsulation film 1309 may be an SiO₂ film or a BPSG film or a combinationof an SiO₂ film and a BPSG film. In the insulation film 1309, anelectrode 1319 is formed in contact with the n+-type drain region 1310and an electrode 1320 is formed in contact with the n+-type sourceregion 1311 respectively as the drain electrode and the source electrodeof the n-MOS transistor. Further, an electrode 1321 is formed in contactwith the p+-type drain region 1312 and an electrode 1322 is formed incontact with the p+-type source region 1313 respectively as the drainelectrode and the source electrode of the n-MOS transistor. Further, abottom electrode 1323 is formed on the rear side of the Si layer 1301.

By using such a metal-substrate SOI structure, it becomes possible toobtain a MOS transistor operable at high speed and consumes littleelectric power.

Meanwhile, it is necessary, in such a substrate including a Cu layerprotected by a TaN film or TiN film, to suppress the temperature ofthermal processing applied to the substrate to 700° C. or less in orderto suppress the problem of diffusion of Cu. Thus, the present embodimentforms the source region or drain region 1310-1313 by applying a thermalannealing process at about 550° C. after the ion implantation process ofAs+, AsF₂+ or BF₂+. Conventionally, the technology of forming ahigh-quality oxide film at a temperature of 700° C. or less has not beenknown. By using the technology of the Kr/O₂ microwave-excitedhigh-density plasma oxidation of the present invention, it has becomepossible for the first time to form a semiconductor integrated circuiton a metal-substrate SOI structure represented in FIG. 14.

When the sub-threshold characteristic is compared between the MOStransistor of FIG. 14 and a conventional MOS transistor that uses athermal oxide film for the gate insulation film, it is inevitable, inthe case a thermal oxide film is used for the gate insulation film, thata kink or leakage appears in the sub-threshold characteristics. When thegate insulation film is formed by the foregoing Kr/O₂ plasma oxidationprocess, on the other hand, an excellent sub-threshold characteristic isobtained.

In the semiconductor integrated circuit device of FIG. 14, it is notedthat the semiconductor layer regions 1314 and 1315 are separated formeach other by forming a mesa-type device-isolation structure, while itis noted that there appears, in such a mesa device isolation structure,a Si crystal surface different from the crystal surface constituting theprincipal surface at the sidewall surface of the semiconductor layerregion 1314 or 1315 that forms a mesa region. By conducting the Kr/O₂plasma oxidation processing explained before, it becomes also possibleto cover the sidewall surface of the mesa region by an oxide film ofuniform thickness similarly to the principal surface. Thus, the MOStransistor of FIG. 14 shows excellent electric properties and providesexcellent reliability.

In the present embodiment, it is also possible to use a Si nitride filmformed by the Ar/NH₃ nitriding processing for the gate insulation film1316 in place of the Si oxide film formed by the Kr/O₂ plasma oxidizingprocessing. In this case, too, it is possible to obtain a highlyreliable semiconductor integrated circuit formed on the metal-substrateSOI structure. For example, excellent electric properties are guaranteedin the case a Si nitride film having a thickness of 4 nm (2 nm in termsof Si oxide equivalent thickness) is used for the gate insulation film1316. Further, the driving power of the transistor increases by abouttwice as compared with the case of using a Si oxide film of 4 nmthickness for the gate insulation film 1316.

[Sixth Embodiment]

FIG. 15 is a schematic diagram showing an example of a substrateprocessing apparatus of the present invention designed for conductingoxidation or nitriding processing to a rectangular substrate such as aglass substrate or plastic substrate.

Referring to FIG. 15, the substrate processing apparatus includes avacuum vessel (processing chamber) 1407 and a Kr/O₂ mixed gas isintroduced in to the processing chamber 1407 from a shower plate 1401 inthe state that the processing chamber 1407 is evacuated. The processingchamber 1407 may be evacuated by a screw groove pump 1402, and thepressure inside the processing chamber 1407 is set to about 1 Torr.

In the vacuum vessel 1407, there is provided a stage 1404 for holding aglass substrate 1403, wherein the stage 1404 is provided with a heatingmechanism. Thus, the glass substrate 1403 is held on the stage 1404 at atemperature of about 30° C.

In the substrate processing apparatus of FIG. 15, a microwave isintroduced into the processing chamber 1407 from a slit of a rectangularwaveguide 1405 via a dielectric plate 1404, and there is formedhigh-density plasma in the processing chamber 1407 as a result. Itshould be noted thereby that the shower plate 1401 functions also as awaveguide for transmitting the microwave emitted by the waveguide 1405laterally in the form of surface wave.

FIG. 16 shows an example of a polysilicon TFT formed by the apparatus ofFIG. 15, wherein the polysilicon TFT of FIG. 16 has a Si oxide film or aSi nitride film as a gate insulation film. Such a polysilicon TFT isused for driving a liquid crystal display device or organic ELlight-emitting device.

First an example that uses a Si oxide film will be explained.

Referring to FIG. 16, the polysilicon TFT is formed on a glass substrate150 and includes an n-type polysilicon pattern 1503 and a p-typepolysilicon pattern 1504 formed on the glass substrate 150 via a Si₃N₄film 1502 as a channel layer of an n-MOS TFT and a channel layer of ap-MOS TFT, respectively.

The channel layers 1503 and 1504 are covered by an insulation film 1509,and a polysilicon gate electrode 1510 is formed on the channel layer1503 via the insulation film 1509. Similarly, a polysilicon gateelectrode 1511 is formed on the channel layer 1504 via the insulationfilm 1509. Further, an insulation film 1512 of SiO₂, BSG or BPSG isformed on the Si₃N₄ film 1502 so as to cover the channel layers 1503 and1504 and further the gate electrodes 1510 and 1511, and a sourceelectrode 1513 and a drain electrode 1514 are formed on the insulationfilm 1512 respectively in contact with the source region 1505 and theregion 1506. It should be noted that the drain electrode 1514 functionalso as the source electrode of the p-MOS transistor formed on thechannel layer 1504 and thus makes a contact with the source region 1507via the insulation film 1512. Further, a source electrode 1515 of thep-MOS TFT is formed on the insulation film 1512, wherein the sourceelectrode 1515 makes a contact with the drain region 1508 via theinsulation film.

As explained before, a polysilicon film is most stable in the state inwhich the Si crystals therein are oriented in the <111> direction, inother words, when the <111> direction of the Si crystals points thedirection perpendicular to the principal surface of the insulation film.In this state, a dense film having excellent crystal quality isobtained. In the present embodiment, the polysilicon film constitutingthe channel layers 1503 and 1504 is formed at the temperature of 350° C.with a thickness of 0.2 μm.

In the present embodiment, the insulation film 1509, which is used asthe gate insulation film, is formed on the polysilicon film by theforegoing Kr/O₂ plasma oxidation processing at the temperature of 400°C. with a thickness of about 30 nm. In the case the insulation film 1509is formed according to such a process, the problem of thinking of theoxide film 1509 in the corner part of the polysilicon patternconstituting the channel layer 1503 or 1504 is avoided, and a Si oxidefilm having a uniform thickness is formed over the planar part and alsoover the edge part.

In the present embodiment, it should be noted that the ion implantationof impurity element for forming the source region or drain region1505-1508 is conducted without causing the ions to pass through the gateoxide film 1509. The ions thus introduced are activated electrically byconducting a thermal annealing process at 400° C. As a result, theentire process for forming the TFT is conducted at a temperature of 400°C. or less.

In the TFT thus formed, an electron mobility of 300 cm2/V.sec or more ora hole mobility of 150 cm2/V.sec is achieved. Further, it was confirmedthat the TFT has a source or drain breakdown voltage and a gatebreakdown voltage of 12V or more. In the case the channel length of theTFT is reduced to 1.5-2.0 μm, it becomes possible to perform ahigh-speed operation with a speed exceeding 100 MHz. Further, the Sioxide film 1509 thus formed showed excellent results with regard toleakage current characteristic and surface state density at thepolysilicon/oxide film interface.

By using the TFT of the present embodiment, a liquid crystal displaydevice or organic EL light-emitting device having the advantageousfeatures of large display area, low cost, high operational speed andhigh reliability, is realized.

[Seventh Embodiment]

FIG. 17 shows the schematic construction of a three-dimensionalsemiconductor integrated circuit device according to a seventhembodiment of the present invention.

Referring to FIG. 17, the three-dimensional semiconductor integratedcircuit has a stacked structure in which a first SOI integrated circuitlayer 1601 and a second SOI integrated circuit layer 1602 are stackedwith each other, wherein the stacked structure thus formed furthercarries thereon a first polysilicon semiconductor device layer 1603 anda second polysilicon semiconductor device layer 1604, and an amorphoussemiconductor device layer and/or a functional layer 1605 is stackedfurther on the polysilicon semiconductor device layer 1604.

Each of the first SOI integrated circuit layer 1601 and the second SOIintegrated circuit device layer 1602 includes a correspondinginterconnection layer, and a digital processing unit, a high-precisionhigh-speed analog unit, a synchronous DRAM unit, a power unit, aninterface unit, and the like are formed in each of the layers by the SOItransistor explained with reference to the foregoing fifth embodiment.

Further, the first polysilicon semiconductor device layer 1603 includesa corresponding interconnection layer, and a parallel digital processingunit, an inter-functional block repeater unit, a memory unit, and thelike, are formed in the first polysilicon semiconductor device layer1603 by using the MIS transistor, the ferroelectric memory device, orthe flash memory device explained already with reference to firstthrough fourth embodiments.

Further, the second polysilicon semiconductor device layer 1604 includesa corresponding interconnection layer, and there is formed a parallelanalog processing unit including an amplifier or A/D conversion unit byusing the TFT explained with reference to the sixth embodiment. Further,a functional unit such as an optical sensor, a sound sensor, a touchsensor, a radio transceiver unit, and the like may be formed in theamorphous semiconductor device layer 1605.

The signals formed in the functional unit of the amorphous semiconductordevice layer 1605 such as the optical sensor, sound sensor, touch sensoror radio transceiver unit are processed by the parallel analogprocessing unit in the second polysilicon semiconductor device layer1604 such as the amplifier or the A/D converter that uses the TFT, andare forwarded further to the parallel digital processing unit or memoryunit formed in the first polysilicon device layer 1603 or in the secondpolysilicon device layer 1604 by using the TFT, the MIS transistor, theferroelectric memory device or the flash memory device.

The signals thus processed are then processed by the digital processingunit or by the high-precision analog processing unit or the synchronousDRAM unit formed in the first SOI integrated circuit layer 1601 or inthe second SOI integrated circuit layer 1602 by using the SOItransistor. Thereby, it should be noted that the inter-functional blockrepeater unit in the first polysilicon integrated circuit layer 1603does not occupy a large chip area even when it is provided with pluralnumbers. Thus, it becomes possible to achieve signal synchronizationover the entire integrated circuit device by providing theinter-functional block repeater unit in plural numbers.

It should be noted that such a three-dimensional semiconductorintegrated circuit device has become possible as a result of thetechnology explained before with reference to the embodiments.

It should be noted that the foregoing description is not limited to the(111) surface of the Si crystal but is valid also with a crystal surfacenear the (111) surface with an offset angle in an arbitrary directionfrom the (111) surface.

Further, the present invention is not limited to the embodimentsdescribed heretofore, but various variations and modifications may bemade without departing from the scope of the invention.

What is claimed is:
 1. A semiconductor device comprising: a Si crystalhaving (111) surface; and an insulation film formed on said (111)surface of said Si crystal, wherein at least a part of said insulationfilm comprises a Si oxide film containing Kr. said Si oxide film beingsubstantially free from crystal defects, and said Si oxide film having asurface state density of 10¹¹ eV⁻¹cm⁻² or less.
 2. A semiconductordevice comprising: a Si crystal having (111) surface; and an insulationfilm formed on said (111) surface of said Si crystal, wherein at least apart of said insulation film comprises a Si oxide film containing Kr,and a Kr concentration level decreases in said Si oxide film from asurface of said Si oxide film to an interface between said Si oxide filmand said Si crystal.
 3. A semiconductor device as claimed in claim 1,wherein said Si oxide film contains Kr with a surface density of 5×10¹¹cm⁻² or less at a surface thereof.
 4. A semiconductor device as claimedin claim 1, further having a gate electrode on said Si oxide film.
 5. Asemiconductor device as claimed in claim 1, wherein said crystal surfaceis formed on a part of a device isolation groove formed on a Sisubstrate.
 6. A Semiconductor device as claimed in claim 1, wherein saidcrystal surface forms a principal surface of said Si crystal.
 7. Asemiconductor device as claimed in claim 1, wherein said crystal surfaceis formed on a surface of a polysilicon film.
 8. A semiconductor devicecomprising: a Si crystal having a (111) surface; and an insulation filmformed on said (111) surface of said Si crystal, wherein at least a partof said insulation film comprises a Si oxide film containing Kr, whereinsaid Kr reduces current leakage and improves breakdown characteristicsof said insulation film when formed on said (111) surface of said Sicrystal and said Si oxide film has a surface state density of 10¹¹eV⁻¹cm⁻² or less.
 9. A semiconductor device as claimed in claim 8,wherein a Kr concentration level decreases in said Si oxide film from asurface of said Si oxide film to an interface between said Si oxide filmand said Si crystal.
 10. A semiconductor device as claimed in claim 8,wherein said Si oxide film contains Kr with a surface density 5×10¹¹ cm⁻² or less at a surface thereof.
 11. A semiconductor device as claimedin claim 8, further comprising a gate electrode on said Si oxide film.12. A semiconductor device as claimed in claim 8, wherein said (111)surface of said Si crystal is formed on a part of a device isolationgroove formed on said Si crystal.
 13. A semiconductor device as claimedin claim 8, wherein said (111) surface of said Si crystal forms aprincipal surface of said Si crystal.
 14. A semiconductor device asclaimed in claim 8, wherein said (111) surface of said Si crystal isformed on a surface of a polysilicon film.